JP2000159855A - Production of polyurethane foam - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce a polyurethane foam excellent in flame retardance, resistance to shrinkage, and dimensional stability by mixing and reacting a polyisocyanate compound with a polyol component mainly comprising a polyol which is obtained by the addition polymerization of an epoxide compound onto an ethyleneamine derivative containing a specified amount of an aminoethylene- group-containing compound having a specified number of N atoms. SOLUTION: An epoxide compound is subjected to addition polymerization at 40-150 deg.C under a pressure of 980 kPa or lower onto an ethyleneamine derivative containing at least 30 wt.% at least one aminoethylene-group-containing compound which has at least four N atoms and is selected from among compounds represented by formulas I and II, thus giving a polyol having an OH value of 100-600 mgKOH/g. A polyol component mainly comprising the above-prepared polyol is mixed and reacted with a polyisocyanate compound in the presence of a blowing agent, a catalyst, and a foam stabilizer to give a polyurethane foam. In the formulas, n and m are each 0 or higher provided n+m is 2-20; and L is 3-20.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a method for producing a polyurethane foam using a novel polyol. More specifically, the present invention relates to a method for producing a rigid or polyurethane foam having an open or closed cell structure, which has excellent dimensional stability and flame retardancy and can be used for producing spray foaming, laminate boards, and the like.

[0002]

2. Description of the Related Art Rigid polyurethane foam has heat insulating properties,
It has excellent moldability and is widely used as a heat insulating material and a structural material for houses and refrigerated warehouses. Regarding its production, HCFC-141b, HCFC-22 and the like are used as foaming agents, but since these foaming agents have an adverse effect on the global environment, reduction and total elimination are planned. Can no longer be used. As a next best measure, a hydrofluorocarbon compound that does not destroy the ozone layer (hereinafter referred to as HFC)
Has been proposed. Basically, practical use of a foaming agent that does not destroy the ozone layer at all is desired. As a technique studied so far, it is general to use only water as a foaming agent and to use carbon dioxide gas generated by a reaction between water and a polyisocyanate compound.

[0003] However, when only water is used as a foaming agent, the resulting polyurethane has a low thermal conductivity or the carbon dioxide gas easily diffuses from the foam into the atmosphere and is easily replaced by air. Foam is shrink resistant,
There is a problem that the dimensional stability is poor. Further, when chlorofluorocarbons such as CFC-11 which have been conventionally used are not used and so-called alternative chlorofluorocarbons such as HCFC-141b or alternative blowing agents such as water which is a chemical blowing agent are used, CFC-11 can be reduced. Compared to using it,
There is also a problem that physical properties such as shrinkage resistance, flame retardancy and dimensional stability of the obtained polyurethane foam are deteriorated.

On the other hand, amine polyether polyols are disclosed in JP-A-54-101899 and JP-A-54-101899.
In JP-A-122396, monoamines, alkanolamines, and polyamines (aliphatic, aromatic, alicyclic or heterocyclic) are used as an active hydrogen compound (initiator), and an alkylene oxide is addition-polymerized thereto. And amine-based polyether polyols. However, these amine-based polyether polyols have a higher reaction rate with a polyisocyanate compound than non-amine-based polyethers, but are not at a sufficient level, and polyurethane foams obtained from the amine-based polyether polyols are difficult to obtain. It is not satisfactory because of poor flammability, shrinkage resistance and dimensional stability.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above problems and to provide a method for producing urethane foam having excellent properties. That is, an object of the present invention is to provide a method for producing a polyurethane foam having excellent flame retardancy, shrink resistance and dimensional stability using a polyol having excellent reactivity with polyisocyanate.

[0006]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to achieve the above object, and as a result, have found that a nitrogen atom is contained in a molecule.
Ethyleneamine derivative containing a specific amount of at least one compound of aminoethylene group-containing compounds having at least one
Polyurethane foam made from a polyol obtained by addition polymerization of an epoxide compound has excellent flame retardancy,
The inventors have found that they have shrink resistance and dimensional stability, and have reached the present invention. That is, according to the present invention, the chemical formula (1)
[Formula 3]

[0007]

Embedded image And chemical formula (2)

[0008]

Embedded image

[In both formulas, n and m are integers of 0 or more, the sum (n + m) of the two is 2 to 20, and L is 3 to 2
At least one of the aminoethylene group-containing compounds having 4 or more nitrogen atoms in the molecule represented by the formula:
A reaction temperature of 40 to 150 ° C. and a maximum reaction pressure of 9
The epoxide compound is subjected to addition polymerization under the conditions of 80 kPa (10 kgf / cm ² ) to have a hydroxyl value of 100 to 600.
a polyol of mg KOH / g is produced, and then a polyol composition containing the obtained polyol as a main component and a polyisocyanate compound are mixed and foamed in the presence of a foaming agent, a catalyst and a foam stabilizer. A method for producing a polyurethane foam is provided.

In the present invention, it is preferable to use a polyol containing at least 30% by weight of the polyol as the polyol composition. When reacting the polyol composition with the polyisocyanate compound, the equivalent ratio of NCO groups in the polyisocyanate compound to active hydrogen in the polyol composition (referred to as NCO index) is as follows:
The reaction is preferably performed in the range of 0.5 to 5. The polyurethane foam obtained by the method of the present invention has excellent shrink resistance, dimensional stability, and flame retardancy. Therefore, it can be widely used as a heat insulating material and a structural material in houses, office buildings, home electric appliances and the like.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. First, a polyol used in the present invention and a method for producing the polyol will be described. Polyol used in the present invention,
It is produced by addition polymerization of an epoxide compound to a specific ethyleneamine derivative.

The ethyleneamine derivative used in the present invention is
It contains an aminoethylene group-containing compound having four or more nitrogen atoms in the molecule as an essential component. Examples of the aminoethylene group-containing compound having four or more nitrogen atoms in the molecule include the compounds represented by the chemical formulas (1) and (2). Of these compounds, those having 4 to 12 average active hydrogen atoms are preferably used.
More preferably, it has 5 to 10 pieces. More preferably, it has six to eight.

A polyol obtained by addition polymerization of an epoxide compound to an ethyleneamine derivative having three or less nitrogen atoms such as ethylenediamine and diethylenetriamine, or a polyol containing the polyol as a main component,
The reactivity with the polyisocyanate compound is not fast enough, and the polyurethane foam obtained therefrom has poor shrinkage resistance, dimensional stability and flame retardancy, and is not satisfactory. Polyols using those having at least 13 average active hydrogen atoms have increased viscosity, poor mixing properties,
It is not desirable because workability deteriorates.

Specific examples of the compounds represented by the chemical formulas (1) and (2) include tetraethylenepentamine,
Chain compounds such as pentaethylenehexamine, 1,4-di (aminoethyl) piperazine, 1- {2- [N- (2-
Aminoethyl)] aminoethyl} -4- (2-aminoethyl) piperazine and other compounds having a piperazine ring. These may be used alone or as a mixture. Examples of the mixture include a high-boiling residue obtained by fractionating ethylenediamine, diethylenetriamine, triethylenetetramine and the like from a crude polyamine (1).
3398 Chemicals, p. 402, Chemical Daily, 1
Published January 28, 998). These commercial products include:
Tosoh Corporation, trade name: Polyate and the like.

In the present invention, an ethyleneamine derivative containing as a main component an aminoethylene group-containing compound having four or more nitrogen atoms and four or more ethylene groups in the molecule is used. The content of the compound in the ethyleneamine derivative affects the reactivity of the obtained polyol with the polyisocyanate compound and the dimensional stability of the polyurethane foam obtained from the polyol. The polyol obtained from the ethyleneamine derivative having a high content of the compound has good reactivity with the polyisocyanate compound, and the polyurethane foam obtained from the polyol has shrinkage resistance, dimensional stability, and flame retardancy. improves.

In view of this, in the present invention, at least one of the aminoethylene group-containing compounds represented by the chemical formulas (1) and (2) and having four or more nitrogen atoms in the molecule is used.
At least 30% by weight, preferably 40%
An ethyleneamine derivative containing 50% by weight, more preferably 50% by weight, is used. Other ethyleneamine derivatives that may be used in combination with the aminoethylene group-containing compounds represented by the chemical formulas (1) and (2) include ethylenediamine,
Examples include diethylenetriamine, tris (2-aminoethyl) amine, piperazine, N- (2-aminoethyl) piperazine and the like.

In the present invention, the epoxide compound which is addition-polymerized to the above-mentioned ethyleneamine derivative includes propylene oxide, ethylene oxide, butylene oxide, styrene oxide, cyclohexene oxide, epichlorohydrin, epibromohydrin, methylglycidyl ether, allyl Glycidyl ether and the like. These may be used in combination of two or more. Of these, propylene oxide, ethylene oxide, butylene oxide and styrene oxide are preferred. More preferably 50% by weight of propylene oxide
The above is a polyol that undergoes addition polymerization.

The reaction conditions for the addition polymerization of the epoxide compound to the ethyleneamine derivative are as follows:
The temperature is 150 ° C, preferably 60 to 130 ° C. When the reaction temperature is lower than 40 ° C., the reaction time of the epoxide compound becomes longer. When the reaction temperature is higher than 150 ° C., the hue of the produced polyol deteriorates. The maximum reaction pressure is 980
It is performed at kPa (10 kgf / cm ² ). More preferably 686 kPa (7 kgf / cm ² ), most preferably 5
It is 88 kPa (6 kgf / cm ² ). If the maximum reaction pressure is higher than 980 kPa (10 kgf / cm ² ), the hue of the produced polyol deteriorates.

A solvent may be used as long as it does not inhibit the polymerization reaction. Examples of such a solvent include aliphatic hydrocarbons such as pentane, hexane, and heptane; ethers such as diethyl ether, tetrahydrofuran and dioxane; aprotic polar solvents such as dimethyl sulfoxide and N, N-dimethylformamide; Water and the like. When a solvent is used, a method of collecting and reusing the solvent after the production is desirable in order not to increase the production cost of the polyol.

As a polymerization method, for example, when propylene oxide and ethylene oxide are used, an ethylene oxide capping reaction in which ethylene oxide is copolymerized in a block after addition polymerization of propylene oxide, and propylene oxide addition polymerization after addition polymerization of ethylene oxide. Propylene oxide cap reaction to copolymerize oxides in blocks, random reaction to randomly copolymerize propylene oxide and ethylene oxide, addition polymerization of propylene oxide, then addition polymerization of ethylene oxide, and then triblock addition polymerization of propylene oxide After the copolymerization reaction, addition polymerization of ethylene oxide, addition polymerization of propylene oxide,
And a triblock copolymerization reaction in which ethylene oxide is addition-polymerized. Either method may be used.

In the addition polymerization of the epoxide compound,
It is also possible to use basic catalysts. Regarding the catalyst charging time, the following two methods are generally used. (A) A method in which a catalyst is added simultaneously with an ethyleneamine derivative to carry out addition polymerization of an epoxide compound (hereinafter abbreviated as a batch addition method). (B) A method of reacting an ethyleneamine derivative with an epoxide compound without a catalyst, adding a catalyst, and further performing addition polymerization of the epoxide compound (hereinafter abbreviated as a post-addition method). (A) and (b) above
Any of the above methods may be used.

Examples of the basic catalyst include alkali metals, alkaline earth metals and amine compounds. Examples of the alkali metals or alkaline earth metals include sodium hydroxide, potassium hydroxide, lithium hydroxide, rubidium hydroxide, cesium hydroxide, magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide and the like. And alkali metal or alkaline earth metal hydroxides. Also, lithium carbonate, sodium carbonate, potassium carbonate, rubidium carbonate,
Alkali metal or alkaline earth metal carbonates such as cesium carbonate, magnesium carbonate, calcium carbonate and barium carbonate are also included. Further potassium bicarbonate,
Bicarbonates such as sodium hydrogencarbonate and cesium hydrogencarbonate are also included.

Examples of the amine compound include triethylamine, dimethylethanolamine, pyridine, methyldimethylamine, tri-n-propylamine, dimethylpalmitylamine, and dimethyloctylamine. These catalysts can be used alone or in combination of two or more.

Usually, after the polyol is produced as described above, a post-treatment is carried out to remove the basic catalyst used. As the post-treatment method, hydrochloric acid, phosphoric acid, inorganic acids such as sulfuric acid, formic acid, acetic acid, oxalic acid, succinic acid, phthalic acid, organic acids such as maleic acid, at least one neutralizing agent selected from carbon dioxide Neutralization treatment method, Levatit MP50
0, Levatit M500, Levatit M504, Levatit MP600, Levatit MP500A (manufactured by Bayer, trade name), Diaion PA406, Diaion PA408, Diaion PA412 (Mitsubishi Chemical Corporation,
(Trade name), Amberlite IRA430, Amberlite IRA458, and Amberlite IRA900 (trade name, manufactured by Rohm and Haas Co., Ltd.).

Also, the Tomix AD series, for example,
Tomix AD-600, Tomix AD-600 (trade name, manufactured by Tomita Pharmaceutical Co., Ltd.), Kyoward series, for example, Kyoward 300, Kyoward 400, Kyoward 50
0, Kyoward 600, Kyoward 600, Kyoward 2000 (trade name, manufactured by Kyowa Chemical Industry), MAGNESO
L (manufactured by DALLAS, trade name) such as a method using a commercially available adsorbent under various trade names, and a method using the above-described neutralization treatment and the adsorbent in combination. Further, the polyol can be purified using water, a solvent inert to the polyol, or a mixture of water and the solvent. For the purpose of stabilizing the quality of the polyol, t-
An antioxidant such as butylhydroxytoluene (BHT) can be added. Usually, the antioxidant is used in an amount of 0.01 to 0.5% by weight based on the polyol.

The polyol obtained by the above method has a hydroxyl value (hereinafter abbreviated as OHV) of 100 to 600 mgK.
OH / g range. Preferably 120 to 58
0 mg KOH / g, most preferably 150-550 mg
KOH / g. When the OHV is less than 100 mgKOH / g, the mechanical strength of the obtained polyurethane foam decreases. When the OHV exceeds 600 mgKOH / g, the viscosity of the polyol increases and the miscibility with the polyisocyanate compound decreases.

Next, a method for producing a polyurethane foam will be described. A polyurethane foam is produced by reacting a polyol which is an active hydrogen compound with a polyisocyanate compound. In the present invention, a polyol produced by the above method or a polyol mixture containing the polyol as a main component (hereinafter, referred to as a polyol composition) is used. As a polyol composition,
Those containing at least 30% by weight of the polyol are preferred.

Other polyols that may be contained in the polyol composition include polyols obtained by adding an epoxide compound to an active hydrogen compound such as polyhydric alcohols, aromatic amines, polyamines, and alkanolamines by the above-mentioned method, and the like. And mixtures of two or more of the above. Further, examples of other polyols include polymer-dispersed polyols, polyester polyols, polytetramethylene glycol, polycarbonate polyols, and polybutadiene-based polyols.

In producing a polyurethane foam, a catalyst and a catalyst are added to the polyol obtained as described above.
A predetermined amount of each of auxiliary agents such as a foaming agent, a foam stabilizer, and a cross-linking agent is mixed according to the purpose to prepare a mixed solution (hereinafter, abbreviated as a resin solution). adjust.
A polyisocyanate is mixed with the obtained resin solution. At that time, the NCO group of the polyisocyanate and the active hydrogen in the resin solution are weighed in accordance with a predetermined equivalent ratio, and adjusted to a predetermined temperature, for example, 20 to 30 ° C. As a molding method, a method of rapidly mixing a resin solution and a polyisocyanate and injecting the mixture into a mold whose temperature is controlled to a predetermined temperature, for example, 20 to 70 ° C., and a method of directly mixing a resin solution and a polyisocyanate compound with each other are used. And a method of spraying and shaping the material (spray method).

As the polyisocyanate compound used for the production of the polyurethane foam, all known polyisocyanate compounds can be used. For example, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, the 80/20 weight ratio of these organic polyisocyanates (TDI-80 /
20), 65/35 weight ratio (TDI-65 / 35) isomer mixture, crude tolylene diisocyanate containing polyfunctional tar, 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 2, Crude MDI containing 2'-diphenylmethane diisocyanate, any mixture of isomers of diphenylmethane diisocyanate, tri- or higher polyfunctional tar
(Polymeric MDI), toluidine diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, and carbodiimide-modified, burette-modified or modified organic polyisocyanate, or
These include polyols and prepolymers modified by monools alone or in combination. These polyisocyanates can be used in a mixture at an arbitrary ratio.

The equivalent ratio between the polyisocyanate and the polyol composition is determined based on the NCO group in the polyisocyanate and the active hydrogen (H) in the polyol composition.
H ratio (hereinafter referred to as NCO index) is 0.5 to
A range of 5 is preferred. When using water as a blowing agent,
The above NCO index range is defined based on the total amount of active hydrogen and active hydrogen in water in the polyol composition.

Known compounds other than chlorofluorocarbons are used as the foaming agent. Here, chlorofluorocarbons are compounds in which hydrogen of hydrocarbons is replaced with halogen such as fluorine or chlorine, and trichlorofluoromethane (CFC-11), dichlorodifluoromethane (CFC-12), monochlorotrifluoromethane (C
FC-13), pentachloromonofluoroethane (CF
C-111), tetrachlorodifluoroethane (CFC)
-112), trichlorotrifluoroethane (CFC-
113), dichlorotetrafluoroethane (CFC-1
14), monochloropentafluoroethane (CFC-1)
15), pentachloromonofluoropropane (CFC-
211). As the foaming agent used in the present invention, for example, hydrocarbon compounds such as cyclopentane and hexane,
HCFC-141b, 2,2-dichloro-1,1,1-
Trifluoroethane (hereinafter referred to as HCFC-123)
Such as halogenated hydrocarbon compounds containing so-called alternative Freon, such as water as a chemical blowing agent,
These foaming agents can be used alone or in combination of two or more. The amount of the foaming agent used is 1 to 40 parts by weight based on 100 parts by weight of the polyol composition. Specifically, when water is used as the foaming agent, it is preferable to use 1 to 9 parts by weight based on 100 parts by weight of the polyol composition. Also, low-boiling hydrocarbon compounds, HCFCs, H
When using at least one foaming agent selected from FCs, FCs, and fluorinated ethers, it is preferable to use 1 to 40 parts by weight based on 100 parts by weight of the polyol composition.

As the catalyst, a conventionally known catalyst for producing a polyurethane such as an amine compound or an organometallic compound may be used. For example, amine catalysts include triethylamine, tripropylamine, tributylamine,
N, N, N ', N'-tetramethylhexamethylenediamine, N-methylmorpholine, N-ethylmorpholine, dimethylcyclohexylamine, bis [2- (dimethylamino) ethyl] ether, triethylenediamine, and salts of triethylenediamine And amine salts such as dibutylamine-2-ethylhexoate. Organometallic catalysts include tin acetate, tin octylate, tin oleate, tin laurate, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dichloride, tin 2-ethylhexylate, lead octanoate, lead naphthenate, naphthene And nickel naphthenate. These catalysts can be arbitrarily mixed and used. Among these catalysts, organometallic catalysts are particularly preferred. The amount used is 0.00 parts by weight based on 100 parts by weight of the polyol composition.
01 to 10 parts by weight. Preferably it is 0.01 to 5 parts by weight.

In the present invention, optional auxiliaries such as a cocatalyst, a flame retardant, a colorant, a filler, a stabilizer and the like can be used, if necessary. Examples of the co-catalyst include carbonate compounds such as ethylene carbonate and propylene carbonate, and phosphorus compounds such as phosphoric acid esters and phosphites.

As the foam stabilizer, conventionally known organic silicon-based surfactants are preferably used. For example, Nippon Unicar Co., Ltd.
Product name: L-501, L-532, L-540, L
-544, L-544, L-550, L-3550, L
-5302, L-5305, L-5320, L-534
0, L-5410, L-5420, L-5421, L-
5710, SZ-1642, SZ-1627, SZ-1
923, etc., manufactured by Toray Silicone Co., Ltd., trade name: SH-
190, SH-192, SH-193, SH-194,
SH-195, SH-200, SPX-253, etc., manufactured by Shin-Etsu Silicone Co., Ltd., trade names: F-114, F-12
1, F-122, F-220, F-230, F-25
8, F-260B, F-317, F-341, F-34
3, F-345, F-347, F-348, F-350
S, manufactured by Toshiba Silicone Co., Ltd., trade name: TFA-42
00, TFA-4202 and the like. These foam stabilizers can be arbitrarily mixed and used. The amount used is 0.1 to 1 part by weight per 100 parts by weight of the polyol composition.
0 parts by weight.

Depending on the purpose, the following crosslinking agents, flame retardants and the like can be used. Examples of the crosslinking agent include ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, 1,3-butanediol,
Polyols such as 4-butanediol, alkanolamines such as triethanolamine and diethanolamine,
Aliphatic polyamines such as ethylenediamine, diethylenetriamine and triethylenetetramine, aniline, 2,4
Aromatic polyamines such as -tolylenediamine and 2,6-tolylenediamine, and compounds having a hydroxyl value of 200 mgKOH / g or more obtained by adding ethylene oxide, propylene oxide or the like to these compounds. The amount used is preferably 0.1 to 10 parts by weight based on 100 parts by weight of the polyol composition.

A flame retardant may be used depending on the purpose of use of the polyurethane foam. Examples of the flame retardant include tris (2-chloropropyl) phosphate, tris (dichloropropyl) phosphate, tris (dibromopropyl) phosphate, tris (2,2-chloroethyl) phosphate, hexabromocyclododecane, and a product manufactured by Daihachi Chemical Co., Ltd. Name: CR-505 and CR-507, trade names manufactured by Monsanto Chemical Co., Ltd .: Phosgard2XC-20 and C-22-R, trade names manufactured by Stoffer Chemical Co., Ltd .: Fyro
11-6 and the like. The amount used is 0.1 to 30 parts by weight, preferably 0.2 to 20 parts by weight, based on 100 parts by weight of the polyol composition.

In the present invention, the ratio of the isocyanate groups to the active hydrogen groups in the resin solution (NCO / H equivalent ratio) is usually in the range of 0.5 to 5, preferably in the range of 1 to 3. Thus, the ratio of the organic polyisocyanate component to the polyol component is determined. If the NCO / H equivalent ratio is less than 0.5, the obtained foam may not have sufficient flame retardancy, and if it exceeds 5, the brittleness is increased and the physical properties are deteriorated.

The polyurethane foam according to the present invention produced as described above has a density of 30 to 40 kg / m.
^When it is about ³ , the shrinkage ratio is 10 to 30%, the dimensional stability is -1 to -5%, the smoke generation coefficient is 80 to 130, and it is excellent in shrinkage resistance, dimensional stability and flame retardancy. Therefore, the polyurethane foam according to the present invention can be widely used as a heat insulating material and a structural material in houses, office buildings, home electric appliances and the like.

[0040]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, which by no means limit the present invention. Unless otherwise specified, “parts” and “%” in the examples indicate “parts by weight” and “% by weight”, respectively. Incidentally, the viscosity of the polyol shown in the examples, hydroxyl value, and shrinkage of the polyurethane foam,
The dimensional stability and the smoke generation coefficient were measured by the following methods.

(1) Viscosity of polyol (cps / 25)
C) According to the test method for polyethers for polyurethane specified in JIS K-1557, it was measured at 25 ° C using a B-type viscometer. (2) Hydroxyl value of polyol (mgKOH / g) It was measured by the method specified in JIS K-1557.

(3) Foam shrinkage (%) Spray foaming is performed on the slate plates described in the examples and comparative examples so that the foam thickness immediately after spraying is 5 ± 1 mm, and the thickness of the foam is measured. . (Form thickness at this time: Fmm). The obtained foam was cooled to an ambient temperature of 0.
The thickness of the foam after leaving it to stand at 5 ° C. for 5 minutes is measured. (The foam thickness at this time: Gmm). The shrinkage of the foam was calculated from the formula {[(FG) / F] × 100}. (4) Dimensional stability (%) of foam Measured according to the method specified in ASTM-D-756. After foaming, the sample was allowed to stand at 25 ° C. for 24 hours. In the measured values, "-" indicates contraction, "+" indicates
The indication means dilation. (5) Smoke emission coefficient of foam Measured according to the method specified in JIS-A-1321. After foaming, the sample was allowed to stand at 25 ° C. for 24 hours.

Production Example 1 304 parts of an ethyleneamine derivative (manufactured by Tosoh Corporation, trade name: polyate) were placed in an autoclave equipped with a thermometer and a stirrer, and 487 parts of propylene oxide were added thereto. To effect addition polymerization. Further, the reaction temperature was maintained and the reaction was continued for 1 hour. Subsequently, 209 parts of ethylene oxide were introduced over 2 hours. The reaction temperature is maintained and the reaction is continued for 3 hours. The obtained polyamine-based polyol had a hydroxyl value of 433 mgKOH / g and a viscosity of 2
It was 3,000 cps / 25 ° C. Let the obtained polyol be the polyol A (EO content 30 weight%).

Production Example 2 152 parts of an ethyleneamine derivative (manufactured by Tosoh Corporation, trade name: Polyate) were placed in an autoclave equipped with a thermometer and a stirrer, 320 parts of propylene oxide was added, and addition polymerization was carried out at 100 ° C. with stirring. did. Further, the reaction temperature was maintained and the reaction was continued for 1 hour. Next, 2 parts of potassium hydroxide were added, and 358 parts of propylene oxide were introduced over 2 hours. The reaction temperature was maintained and the reaction continued for 2 hours. Subsequently, 170 parts of ethylene oxide were introduced over a period of 2 hours. The reaction temperature was maintained and the reaction was continued for 3 hours. After completion of the polymerization, the mixture was neutralized, dehydrated and filtered to purify. The obtained polyamine-based polyol had a hydroxyl value of 230 mgKOH /
g, viscosity 2,600 cps / 25 ° C. The obtained polyol is referred to as polyol B (EO content: 20% by weight).

Production Example 3 152 parts of ethylenediamine was placed in an autoclave equipped with a thermometer and a stirrer.
6 parts were added and addition polymerization was carried out at 100 ° C. with stirring. Further, the reaction temperature was maintained and the reaction was continued for 1 hour. Next, 2 parts of potassium hydroxide was added, and 555.6 parts of ethylene oxide was added to 2 parts.
Introduced with time. The reaction temperature was maintained and the reaction was continued for 3 hours. After completion of the polymerization, the mixture was neutralized, dehydrated and filtered to purify. The resulting polyamine polyol has a hydroxyl value of 45.
It was 0 mgKOH / g and the viscosity was 900 cps / 25 ° C. Let the obtained polyol be polyol C (EO content 50 weight%).

Production Example 4 Into an autoclave equipped with a thermometer and a stirrer was charged 206 parts of diethylenetriamine, and the temperature was raised to 115.degree. After 4.9 parts of potassium hydroxide was added and mixed, 978 parts of propylene oxide and 420 parts of ethylene oxide were gradually introduced in this order. After completion of the polymerization, the mixture was neutralized, dehydrated and filtered to purify. The obtained polyamine-based polyol had a hydroxyl value of 350 mgKOH / g and a viscosity of 600 cps / 25 ° C.
Met. Let the obtained polyol be polyol D (EO content 30 weight%).

<Production of Polyurethane Foams> Examples 1 and 2 and Comparative Examples 1 to 2 A polyol, a foam stabilizer, a catalyst, a flame retardant, and a foaming agent were mixed in accordance with the mixing ratio shown in Table 1 and the temperature was adjusted. 25 ±
The temperature was adjusted to 1 ° C., and the polyisocyanate previously adjusted to 25 ± 1 ° C. was mixed so as to have the NCO index shown in Table 1. After adjusting the surface temperature of the slate plate of 900mm length, 900mm width and 6mm thickness to 0 ° C,
At an ambient temperature of 0 ° C., the mixture was spray-foamed on the slate plate so that the thickness after foaming became 50 mm, to produce a polyurethane foam. The flame retardancy, dimensional stability, and shrinkage of the obtained polyurethane foam were measured by the above methods. The results are shown in [Table 1].

The following raw materials were used in addition to the amine polyol. Polyol E: commercially available polyol (manufactured by Mitsui Chemicals, Inc.
Brand name: NE-410, hydroxyl value 415mgKOH /
g) Polyisocyanate A: Polymethylene polyphenyl polyisocyanate (trade name: Cosmonate M-50, NCO%: 31.7, manufactured by Mitsui Chemicals, Inc.) Foam stabilizer: Silicone foam stabilizer (Nihon Unicar Co., Ltd.) Made,
Trade name: SZ-1642) Catalyst: Mixture of N, N ′, N ″ -tris (dimethylaminopropyl) hexahydro-s-triazine and potassium octylate (trade name: POLY, manufactured by Air Products)
CAT-42) Flame retardant: tris (β-chloroisopropyl) phosphate Blowing agent: 1,1-dichloro-1-fluoroethane (H
CFC-141b)

[0049]

[Table 1]

<Consideration of Examples> As shown in Examples 1 and 2, the polyurethane foam according to the present invention using polyamine-based polyols as a main raw material has low foam shrinkage even under low temperature conditions and is dimensionally stable. Excellent in fire resistance and flame retardancy. On the other hand, the existing polyurethane foams using an amine-based polyol as a main raw material (Comparative Examples 1 and 2) cannot be said to have good foam shrinkage, dimensional stability, and flame retardancy.

[0051]

According to the present invention, in producing a urethane foam,
HCFC-141b is used without using chlorofluorocarbons such as CFC-11 generally used in the past.
When an alternative blowing agent such as so-called alternative Freon or a chemical blowing agent such as water is used, the foam shrinks as compared with the case where CFC-11 is used, and the flame retardancy of the obtained foam,
Physical properties such as dimensional stability were inferior. On the other hand, the polyurethane foam according to the present invention using a polyamine-based polyol has good shrinkage resistance, excellent flame retardancy, excellent dimensional stability and the like even without using chlorofluorocarbon as a blowing agent at all. Therefore, the polyurethane foam according to the present invention can be widely used as a heat insulating material and a structural material in houses, office buildings, home electric appliances and the like.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Satoshi Tamura 2-1-1 Tango-dori, Minami-ku, Nagoya-shi, Aichi Prefecture Inside Mitsui Chemicals, Inc. (72) Inventor Saku Izugawa 2-1-1 Tango-dori, Minami-ku, Nagoya-shi, Aichi Address Mitsui Chemicals, Inc. F-term (reference) 4J034 BA05 DA01 DB03 DB07 DF01 DF02 DG03 DG04 DG05 DG06 DG09 DG10 DG12 DG14 DG18 DG20 DG23 GA06 GA33 HA01 HA02 HA06 HA07 HB05 HB06 HB08 HC03 HC12 HC61 HC63 HC64 KC18 KC35 KD02 KD12 KE02 NA02 NA03 NA06 NA08 QA01 QA02 QB17 QB19 QC01 QD06 RA10

Claims (7)

[Claims] (1) Chemical formula (1) And the chemical formula (2) [Chemical formula 2] [In both formulas, n and m are integers of 0 or more, the sum (n + m) of the two is 2 to 20, and L is an integer of 3 to 20]. An ethyleneamine derivative containing at least 30% by weight of at least one compound of at least four aminoethylene group-containing compounds,
Reaction temperature 40-150 ° C, maximum reaction pressure 980 kPa
(10 kgf / cm ² ), an epoxide compound is subjected to addition polymerization to give a hydroxyl value of 100 to 600 mg KOH.
/ G, and then mixing and foaming a polyol composition containing the resulting polyol as a main component and a polyisocyanate compound in the presence of a foaming agent, a catalyst and a foam stabilizer. A method for producing a polyurethane foam. 2. The method for producing a polyurethane foam according to claim 1, wherein an epoxide compound containing at least 50% by weight of propylene oxide is used as the epoxide compound. 3. The method according to claim 1, wherein the polyol composition contains at least 30% by weight of the polyol. 4. The method for producing a polyurethane foam according to claim 1, wherein the polyol composition and the polyisocyanate compound are reacted in an NCO index range of 0.5 to 5. 5. The amount of the foaming agent used in the polyol composition 1
The method for producing a polyurethane foam according to claim 1, wherein the amount is 1 to 40 parts by weight based on 00 parts by weight. 6. The amount of the catalyst used in the polyol composition 10
The method for producing a polyurethane foam according to claim 1, wherein the amount is 0.0001 to 10 parts by weight based on 0 part by weight. 7. The amount of the foam stabilizer used in the polyol composition 1
The method for producing a polyurethane foam according to claim 1, wherein the amount is 0.1 to 10 parts by weight based on 00 parts by weight.